Controlling catalyst-oil ratio by use of a venturi



,'July l5, 1947.` D. l... CAMPBELL coNTRoLLmG cATALYsT-OILRATIO BY USE oF A VENTUR'I' Filed nay 9,y 19'41 3 Sheets-Sheet l NNI WNN

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NIGNLN July 15, 1947.

v1:. l.. CAMPBELL CONTROLLING' CATLYST-OIL RTI BY USE- 0F A VENTRI 3 Sheets-Sheet 2 l Non.

'Filed nay s. v1941 NNN. A .N NN

D. L. CAMPBELL f 'July 15, 1947.`

CONTROLLIING CATALYST-OIL RATI BY,USE OF A VENTURI Filed nay 9, 1941l -5 sheets-snaai s Patented July l5, 1,9 47

coN'rRoLLING cATALYs'r-on. mno Bv css or A VENTURI Donald L. Campbell, Short Hills, N. J., assignor to Standard Oil Development Company, a cor poration of Delaware Application May 9, 1941, Serial No. 392,606

lclaim. y(cl. 19e-52) This invention relates to catalytic conversions of hydrocarbons, wherein powdered catalysts are used and more particularly relates to controlling the ratio of catalyst to hydrocarbon oil to be converted. v f

According to this invention, powdered catalyst from. a catalyst hopper is fed into a standpipe, amigas such as steam or the like is introduced into the standpipe at various points to aerate the catalyst mass and to maintain it in a iluidized condition so that it takes on the properties f 'a iluid. lThe standpipe of iluidized catalyst provides a head of pressure which is utilized to force the catalyst into a mixing chamber in a pipe where it mixes with a flowing stream of hydrocarbons in vapor form at a controlled rate and with or without steam and the suspension of catalyst inthe hydrocarbon vapors is then passed through areaction zone.

The reaction zone is of a larger diameter than the inlet pipe which feeds the mixture to the reaction zone and due to the low velocity of the mixture through the zone, there is a slippage between the catalyst particles and the hydrocarbon vapors and the vapors pass through the reaction zone at a higher velocity than the catalyst particles. However, the velocity of the mixture through the reaction zone is sulclently high to prevent settling of the catalyst particles on the oor of the reaction zone.

The reaction products and catalyst particles leave the reaction zone through an outlet pipe and are passed to a separating means for separatingcatalyst particles from reaction products in vapor form. This outlet pipe is provided vwith a venturi associated with control means to rconthrough the venturi. The static pressure dier- The catalyst fparticles separated from reac-l tion products in vapor form have carbonaceous deposits which reduce the activity of the catalyst and itk is desirable toregenerate the catalyst par.. ticles. ,The separated catalyst particles yare introduced into another standpipe which is aerated by the introduction of steam or other suitable sas into the standpipe at spaced points. The suspension ot fouled catalyst particles is passed withv air through a regeneration zone where the carbonaceous material is burnt off from the catalyst particles and the regenerated catalyst particles are then introduced into the catalyst hopper for introduction into the first standpipe above described. v'

In the drawing: f

Figure. 1 represents one form of apparatus for carrying out my invention: Figure 2 diagrammatically represents the control means associated with the venturi for controlling the catalyst-oil ratio; y

Figure 3 represents a detail in vertical cross section taken substantially on line III-III of the cylinder in Figure 2; and V Figure 4 represents a horizontal cross section taken on line IV-IV of the cylinder to show the slot in the bottom of the cylinder.

It is to be understood that the invention is not to be restricted to the apparatus shown as other forms of apparatus may be used.

Referring now to the drawing, the reference character i0 designates a line through which hydrocarbon oil to be converted is passed by means of pump 2 at a controlled rate. The hydrocarbon oil may be any usual cracking stock.

such as gas oil, or the like. The hydrocarbon oil is passed through a heating coil ll in the heater i6 to substantially completely vaporize the f oil and to raise it to the desired temperature. Steam may be added at a controlled rate as, for example, through line l1 to aid in vaporization of the oil.

The oil vapors withor without steam are passed through line I8 and mixed in chamber or zone 22 with powdered catalyst introduced from the standpipe '2L The powdered catalyst is vmaintained in a iluidized condition in vthe standpipe 24 as will be hereinafter described in greater de tail.A The Ipowdered catalyst is preferably of particles of a size between 1 and 150 microns and may comprise any suitable cracking catalyst such as natural or acid treated clays., synthetic clays, synthetic gels containing silicaand alumina Aor synthetic gels containing silica and magnesia, or the like.

The mixture oi oil vapors and catalyst at a conversion temperature is passed through line 2l and into the bottom of reaction zone 2,8.v The reaction zone isV anyenlarged. chamber :having a diameter much greater than thediameter of the pipe 28. V The `velocity of the stream through the reaction zone and through the system is relatively low so that the pressure drop through the system is small. Due to the relatively low velocity, the

hydrocarbon vapors pass through the reaction zone at a-greater rate than the catalyst particles and there is a higher concentration ot catalyst 3 in oil vapors in the reaction zone. At the same time, the vapors and catalyst particles are maintained in a turbulent condition so that the temperature in: the reaction zone is substantially uniform throughout the entire zone. While the velocity permit-s concentrationV of the catalyst particles in the reaction zone, it is to be noted that the velocity is sufilciently high to prevent settling of the catalyst particles on the floor of the reaction zone.

The reaction products and the catalyst particles leave the top of the reaction zone 28 through line 32 provided with a venturi 34 and are passed to a separating means 38 which is shown in the drawing as a cyclone separator for separating catalyst particles rfrom reaction products in vapor form.

'Ihe venturi 34 comprises a control means which is associated withthe valve 38 at the bottom of the standpipe 24 to control the amount of catalyst being' introduced into the mixing chamber 22 from the standpipe 24. The venturi and assoelated part-s will be described in greater detail hereinafter.

In the separating means 38 catalyst particles are separated from vapors, the catalyst particles dropping into a hopper 42 and the vapors passing `overhead through line 43. Steam may be introduced into the bottom portion of the hopper 42 by means of line 44. The catalyst particles after having passed through the reaction zone 28 are coated with carbonaceous deposits which reduce the activity of the catalyst particles and it is desirable to remove these carbonaceous deposits and regenerate the catalyst particles. In some instances the catalyst particles may be returned to standpipe 24 for recycling in the process Without regeneration.

The catalyst particles are withdrawn from the bottom of the hopper by means of a star feeder 48 and are passed through line 48 to a mixing chamber 52 where they are suspended in a gaseous fluid such as steam introduced into the mixing chamber 52`by means of line 84. The suspension of fouled catalyst particles in steam or the like is passed through line 58 and introduced into the upper part of a collecting chamber 82. The collecting chamber 82 is 'provided with a baffle 84 which functions to separate catalyst particles from the gaseous carrier, the catalyst particles dropping into the lower part of the chamber 82.

The reaction products in vapor form leaving the separating means 38 through line 43 are introduced into a second separating means 88 which is shown as a cyclone separator for separating additional amounts of catalyst particles from the reaction products in vapor form. Sepa rating means 88 form the upper ypart of collecting chamber 82. The separated catalyst particles drop into the collecting chamber 82. The separated' reaction products pass overhead through line 18 andare further treated in any suitable manner such as in a fractionating system to separate desired products including gasoline from the reaction products.

The catalyst particles in the lower part of the collecting chamber 82 are introduced into a second standpipe 'I2 which communicates with the bottom of the chamber '82. Iny order to aerate the mass of fouled catalyst particles, steam or other suitable gas is introduced into thestandpipe 12- by means of manifold 14 and spaced lbranch lines 18, 18 and82.

The aerated catalyst particles are introduced 4. into a-mixing chamber 84 where they are mixed with air or other oxidizing agents introduced by` Vmeans of line |l8.\ The suspension of catalyst particles inthe oxidizing agent is passed through line 88 and introduced into the bottom of 'a regeneration zone 92. The regeneration zone is an enlarged chamber which is similar in construction tothe reaction zone 28. Due to the relatively low velocity of the stream through the chamber there is a slippage between the regenerating gases and the catalyst particles and the regenerating gases pass through the regeneration zone at a faster velocity than the catalyst particles. However, the velocity of the stream through the reaction zone is sufiicient to prevent settling of the catalyst particles on the floor of the regeneration zone. It is important to control the temperature of the catalyst particles ,during regeneration and the control of this temperature will be presentlyv described.

The regenerated catalyst particles and regen-4 erating gases leave the regeneration zone throughv line 83 and are introduced into a separating means 94 which is shown as a cyclone separator for separating catalyst particles from regenerat-l The regenerating gases pass overhead' Fresh catalysty may be introduced into the cata-` lyst hopper 98 by means of line |82. The regenerated catalyst particles together with any added fresh catalyst particles are introduced into the upper part of the standpipe 24 which communicates with the bottom portion of the hopper 98.

In order to maintain the catalyst particles in' fluidized condition, any suitable gas such as steam. or the like is introduced into the standpipe 24. The gas is introduced into manifold |88 which communicates `with branch lines |88, ||8 and |I2 for introducing the fluidizing medium into the catalyst mass in the standpipe at spaced points along the length of the standpipe.

Returning now to the regeneration zone, the method of controlling the temperature during regeneration will be described. A third standpipe H4 is'shown as communicating with the bottom of the vcatalyst hopper 98. Regenerated catalyst,

particles from the hopper 98 are also introduced into the standpipe ||4. The catalyst particles in the standpipe |I4 are maintained in a fluidized condition by introducing a gaseous medium such as air into the catalyst mass in the standpipe ||4.

' The gaseous medium is introduced into a manifold ||8 provided with branch lines ||8, |22 and |24 for introducing the gaseous medium into the standpipe H4 at spaced points along the length of the standpipe.v

The regenerated catalyst in iiuidized condition from standpipe ||4 is introduced into a mixingy chamber |28 where it is further mixed with air or other oxidizing medium introduced into the mixing chamber by means of line |28. The catalyst particles from the mixing chamber |28 are passed through a cooler |32 for reducing their temperature and they are then passed through line |34 and introduced into the regeneration zone 92 along with fouled catalyst from line 88. In

this way the temperature of the catalyst particles in the regeneration zone is controlled and is prevented from rising above about 1200 F. A bypass line, |38, is provided to control the temperature of-the stream entering regeneration zone 82.

If the fouled catalyst particles passing through line 88 are at too low a temperature, hot regenerated catalyst particles from .the mixing chamber |28- are b'y-passed around the coolerv |32, passed through line |38 and mixed with the fouled catalyst particles passing through line 88 before they are introduced into the regeneration zone 92.

Slide valves |40, 38 and |42 are provided for the bottomof the standpipes 4, 24 and 12, respectively, for control purposes. 'Ihe catalyst particles collected in hoppers 82 and 98 are preferably aerated or uidized as shown by extensions |44 and |45 of lines 14 and |08, respectively.-

As above pointed out, for a given velocity the static pressure diierential for a gas passing through a venturi will vary with the density of the gas. According to this invention, gasesv and solid particles are passed through the system but since the mixtureor suspension oi' catalyst particles in a gaseous carrier assumes the characteristics of a fluid or gas, with a given concentration of catalyst particles in a gas, the iluid stream will have a certain density and this will give a certain static pressure differential through the venturi 34. If the concentration of the catalyst particles varies in the gaseous carrier during the process for any reason, the density of the stream willalso vary and the static pressure dierential through the venturi 34 will vary. This variation causes operation of the valve at the bottom o1 standpipe 24 to control the amount of catalyst being introduced into mixing chamber 22.

According to my invention, the Venturi control is set for a desired ratio of weight rates of flow of catalyst -particles toK oil and variations from this selected ratio are compensated for by the controlling means associated with the venturi 34. The mechanism whereby the venturi 34 controls the amount of catalyst introduced into the mixing chamber- 22 from the standpipe 24 will now be described.

As shown in Figure 2 of the drawing, the line |52 connects with the pipe 32 leaving the reaction zone 28 preferably at least one-half pipe diameter preceding the mouth of the inlet section of the venturi 34, and the line |54 connects with the venturi 34 at the reduced or throat position |55 at the minimum cross-sectional area. As the catalyst particles and vapors or gases pass through the pipe 32 and through the venturi 34, there' is a static pressure diierential created due to the restricted area ,of the throat |55 in the venturi. This static pressure diierential varies with` the density of the suspension passing through the venturi andits velocity. The static pressure diierential caused by the venturi is used to actuate a diaphragm-operated valve |58 through lines |52 and |54. In order to prevent catalyst particles from entering and plugging the lines |52 and |54, bleed lines |51 and |58 are provided for bleeding in a small amount of gas so as to insure that at all times there is a ilow of gas from line |54 into Venturi throat |55 and from line |52 into line 32. This flow is maintained at so low a rate in each case, as compared with the diameter of the lines |54 and |52 in question, that the respective pressures in lines |54 and |52 are, substantially constant throughout their lengths.

A change in the static pressure diierential be- |82 and which extends through stuflingboxes |88 and |12 into and through line |14 and terminates in a valve disc |18 which seats against valve seat |18. Thus, the increase in the abovementioned pressure diilerential causes disc |18 to approach seat |18 and tends to reduce the` ow in line |14. y

Air is -supplied to line |14 from any suitable source of compressed air through line |82. The pressure of the air in line |14 is regulated as follows: Line |14 is connected by line |84 to the space under a diaphragm |88 of aidiaphragmoperated valve |82, the space above the diaphragm being open to the air through line |94. The pressure in line |14 is used to push the diaphragm |88 upward against the resisting torce of spring |98 and to thereby lift valve stem |98 which is secured to the under side of diaphragm |88 and extends downward therefrom through stumng boxes 202 and 204 into reducing valve 208 where it terminates in a valve disc 208 which closes against valve seat 2|2. As will be seen from the drawing, an increase in pressure in line |14 tends to shut the valve 208 and thereby decrease the ow from line |82 into line |14. By this means it is possible to maintain a constant air pressure in line |14 even though the air pressure in the source line |82 is somewhat variable. i

Sincethe air pressure in line |14 is substan tially constant 4and since it has been-shown that an increase in the static pressure dierential across the venturi ten'ds to close the valve disc |98 against the valve seat |18, it is evident that an increased Venturi static pressure differential tends to decrease the flow in line 2| 4 extending beyond valve seat |10, but this line is connected to a chamber 2|8 of a diaphragm operated valve 2|8, thechamber 2|8 having a restricted opening 222 to the atmosphere so that decreasing this flow tends to decrease the pressure in line 2|4 and in chamber 2|8. Chamber 2|8- is to the left of diaphragm 224, and to the right ofthe diaphragm is a'. chamber 228 open to the atmosphere through line 228. A decrease in the pressure in the left chamber 2|8 tends to cause the diaphragm 224 to move to the left because the force tending to compress the diaphragm 224 against the spring 221 is reduced. The leftward movement of the diaphragm 224 causes a leftward movement of the valve stem 229 secured to the left sideof diaphragm 224 andwhich extends through stulng boxes 232 and 234 into valve 238 and terminates in valve disc 238 which seats against valve seat 242. This leftward movement I of the valve seat tends to open the valve 238.

Oil or water is stored in an atmospheric reservoir 244 and is pumped from this reservoir through line 245 by an ordinary centrifugal pump reducing valves may be as indicated, diaphragm-4 Y operated valves 212 and 214 similar in construc-- saggia? tion to the diaphragm-operated valves above described and including diaphragm 218, and springs 211 fior operating the valves. The diaphragm-operated valves `are set for the desired pressures vand higher pressures will` open valves 254 and 282 to maintain the desired pressures in the chambers 248-and 256.

Each valve is, of course, arranged so that an increase in the pressure in the preceding chamber tends to open the valve. The two chambers are connected through lines 218 and 282, respectively, to the two opposite ends of a cylinder 284 in which moves a piston 288 attached to stem 288 of valve 38. The medium pressure chamber 258 is connected to the side of the cylinder adjacent to the valve 38 and the connecting line 218 is made sufciently large so that the pressure at that end of the cylinder 284 is substantially the same as in the medium pressure chamber 258 and is therefore maintained constant.

I will next describe means to temporarily raise the pressure in the other end of the cylinder 284,

near line 282 above that in the medium pressure chamber 258 or to lower it below the pressure in the medium pressure chamber and to thereby cause the piston 288 to move in such a direction as to partially close or open. respectively, the valve 38. I will also describe means by equalization of the pressures on the opposite sides of the piston 288 to cause this movement to stop when it has reached a certain desired position.

In the lower part of cylinder 284 there is a slot 292 which opens into a collecting line 294. This collecting line is vented to the air through line 298 and is drained through line or drain 298 to the atmospheric reservoir 244 which is at a lower elevation. It should be noted that the slot 292 as shown in Figure 3 is intended to oier a restriction to the flow of oil or water from the cylinder 284 to the atmospheric reservoir 244 and that once the liquid has passed through this restriction or slot it is collected inthe line 294 which is large enough and well enough vented so that line 294 will not run full and the pressure at all points on the downstream side of the restriction 292 is atmospheric. The slot 292 may be uniform in width throughout its length but is preferably triangular in shape with the point of the triangle at the end of the cylinder 284 connected to line 282 and the base of the triangle adjacent the other end of the cylinder 284 connected to lin'e 218 so that the width of the slot gradually increases toward the left in Figure 2. Figure 4 diagrammatically shows a plan view of the preferred form of slot 292.

The Pressure inthe end of cylinder 284 connected to line 218 is maintained substantially constant because of the large size of line 218 and the small iiow through line 218 required to supply the flow through the restriction 292 back to reservoir 244. Thus, no matter what the position of the piston 288, that is, no matter how much' ofr the slot 292 is uncovered by the piston 288 on the side of the cylinder 284 connected to line 218,

from lhigh pressure cylinder 248 through line 282.

to the other end of ycylinder284 is restricted by the valve 238. For a given position of the piston 288, partially opening or closing the valve 238 increases or decreases, respectively. the iiow through line 282 and since the amount of the slot 292 uncovered on this side of the piston 288 remains constant, this increase or decrease in flow'through line 282 causes an increase or decrease, respectively, in the pressure in the adjacent end of the cylinder 284. Thus, if the piston 288 is originally taken to be at rest due to balancing of the pressures on opposite sides thereof, the opening or closing of valve 238 would tend to close or open,'respectively, the valve 88.

Now let us suppose that valve 238 has been partially opened to cause movement of the piston 288 in the direction to close valve 38. Then, as this movement of the piston 288 proceeds, more of the slot 292 is uncovered on theside. f the cylinder 284 which is connected to the line 282. This increase in the slot `area 292 tends to decrease the pressure differential across fthe slot and thereby decrease the pressure in that end of the cylinder 284. Thus, eventually a condition is reached inA which the pressures on both sides of the piston 288 are again equalized, at which time the movement of the piston 288 stops. In order to maintain a maximum differential pres-- sure between the two sides of the Piston 288 up to within a short distance from the desired point .of stoppage of movement of the piston, it is prebe extended beyond the limits of piston and valve' travel.

Small holes may be provided in the ends of cylinder 284 draining to the atmospheric reservoir' 244 to cushion full motion of the piston 288. Emergency connections may be provided, forA example, from the high Pressure chamber 248-to the high pressure side of cylinder 284 to close the valve 38 rapidly and completely by moving piston 288 to the left in the drawing.

A consideration of the above-described equipment as a whole will show that it can be pro--4 portioned in size and designed` in detail so that' a small change in the static pressure diierentlal in the venturi will produce a large movement of the valve stem 288 and thatfor every value of the Venturi static pressure diilerential there will result a certain position of th'e valve stem 288. Thus, the equipment indicated willinsure controlling the iiow of catalyst into the mixing zone or chamber 22 so as to maintain within a' small variation the density of the material" owing through the venturi 34.

While I have shown certain preferred control and regulating devices, it is to be understood that lother controllers and regulators may be used for changing the position of th'eslide valve 38 in response to changes in static pressure difierentials occurring when the fluids passing through line 32 are passed through the venturi 34.

Instead of placing venturi 34 in the outlet line bottom portion of the-reaction chamber 28 may be used and the static pressure differential of catalyst delivered to mixing chamber 22 from standpipe 24. In the event that the grid 302 is med as a means to create a static pressure differential, the venturi 34 is dispensed with and line |52 is connected with the reactor 23 below grid 302 and line |54 is connected with the re actor 28 just above grid 302.

The invention will now be more specically described in connection with catalytic cracking of hydrocarbons. A gas oil having an A. P. I. gravity of 26.7 is vaporized and passed together with 1.5 lbs. of distillation steam per barrel through line i8. The catalyst to be used is preferably an acid treated bentonite clay, which is finely 4divided into particles of a size between 1 and 150 microns. Th'e catalyst is uidized in standpipe 24.

The valve 36 is opened to give a catalyst-oilv ratio of rates of ow of about 4 to 1 by weight. The temperature of the catalyst-oil suspension in line 32leaving the reactor. 28 is about 925 F., the pressure is about 11 lbs. per sq. in. gauge and the velocity is about 32 feet per second. The velocity in the throat of the venturi is about 138 feet per second. With the control means set for this catalyst-oil ratio and with normal operation there will be no changes or adjustments necessary in the control means. 'I'he static pressure differential at the venturi is about 1 pound per square inch.

However, if the catalyst-oil ratio is changed for any reason' the automatic means comes into play to readjust the ratio to the original gure'.

'For example, if less catalyst is delivered per weight of oil vapors to mixing chamber 22, the density of the suspension in line 28, reactor 20 and line 32 will be less and the static pressure differential at the venturi 34 will be less. 'I'his lessened pressure differential will be transmitted and translated by the control means to cause movement of the piston 286 and valve 36 to the right in Figure 2 and' deliver more catalyst to the mixing chamber 22. This will increase the density cf the stream ilowing through line 28, reactor 28 and line 32 so that the static pressure drop through the venturi is again 1 pound per square inch and the ratio of catalyst to oil will be automatically maintained.

If too much catalyst is being introduced into mixing chamber 22, the static pressure difierentiai through venturi -34 will increase beyond th'e desired ngure and the control means will function to lower the static pressure dierentiai to the desird ligure to correspond to the desired catalystoil ratio by weight.

It should be noted that the size of catalyst particles used ail'ects the static pressure diiierential of the venturi and that calibration is desirable in order to measure accurately the ratio of weight rates of flow of catalyst and oil. However, for control purposes the ratio of weight rates of ilow of catalyst and oil need not be known accurately. It will be found by trial and error that a certain static pressure diierential in the venturi is desirable for a certain rate oi' ow of oil feed to the unit (with a fixed proportion of steam).

My invention may be used for catalytic cracking oi hydrocarbons, catalytic polymerization of hydrocarbons, catalytic dehydrogenation, aromatization, alkylation and other catalytic conyio versions of hydrocarbons where a suspension of catalyst particles is used in a hydrocarbon gas' or vapor. v

While a specific example of the preferred form of the invention has been given with respect to catalytic cracking, it is to be understood that this example is by way of illustration only and my invention is not to be restricted thereto as modifications and changes may be made without departing from the spirit of my invention.

In particular my invention may be used for catalytic reactions carried out in apparatus other than the preferred form above-described. As regards the reactor provided, whereas the preferred form of the reactor is of larger diameter than the inlet pipe which feeds the mixture to the reaction zone, it is possible in certain cases to use a reactor no larger in diameter than the inlet pipe. Such a reactor may be relatively long and may be arranged, for example, in the form of a spiral coil or successive vertical or horizontal runs of pipe connected by U bends.

Also, although in the preferred form of the invention a standpipe of rluidized catalyst is used to provide the head of pressure required to force the catalyst into the mixing chamber before the reactor, as an alternative the catalyst may be charged through a lock hopper system into a chamber with a bottom outlet leading through a relatively short length of line to the catalyst feed control valve. By means of suitable arrangements known in the art, gas pressure may be imposed upon the hopper system sucient to cause the catalyst to iiow downward through the outlet and through the vcatalyst feed control valve into the above-mentioned mixing chamber.

Iclaim:

A method of catalytically converting hydrocarbons which includes maintaining a desired powdered catalyst to oil ratio which comprises delivering powdered catalyst to a mixing zone as a fluidized stream from a standpipe, mixing a hydrocarbon vapor stream with the stream of powdered catalyst in said mixing zone, passing the mixed stream as a suspension through a combination of a restriction and a* reaction zone in series and-then a separating zone to separate reaction products from catalyst and controlling "the rate of iluidized catalyst delivery to said mixing zone by a valve in said standpipe which valve is in turn controlled by the static pressure differential through said restriction.

DONALD L. CAMPBELL.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS 

